Perfume compositions containing 6-propyl-3-cyclohexene carbaldehydes

ABSTRACT

PERFUME COMPOSITIONS CONTAINING SUBSTITUTED 6-PROPYL3-CYCLOHEXENE CARBALDEHYDES WHICH ARE PREPARED BY REAC!ING 2-HEXENE-1-AL WITH PENTADINES OR HEXADINES BY MEANS OF A DIELS-ALDER-REACTION.

United States Patent 3,812,059 PERFUME COMPOSITIONS CONTAINING 6-PROPYL-3-CYCLOHEXENE CARBALDEHYDES David de Rijke, Naarden, andHarmannus Boelens,

Huizen, Netherlands, assignors to Naarden International N.V. No Drawing.Filed Apr. 27, 1972, Ser. No. 248,127 Claims priority, applicatgtinNetherlands, Apr. 27, 1971,

5711 Int. Cl. A61k 7/00; Cllb 9/00 US. Cl. 252-522 8 Claims ABSTRACT OFTHE DISCLOSURE Perfume compositions containing substituted 6-propyl-3-cyelohexene carbaldehydes which are prepared by reacting Z-hexene-l-alwith pentadienes or hexadienes by means of a Diels-Alder-reaction.

The invention relates to a process for the preparation of perfumecompositions and perfumed products which contain as an odor impartingmaterial an unsaturated alicyclic aldehyde together with othercomponents usually employed for this purpose. More particularly theinvention relates to perfume compositions containing 6-propyl-3cyclohexene carbaldehydes of the formula CHO 11-CaH7 HaC CHO CHa3,5,6-trimethy1-3-cyclohexene carbaldehyde of the formula and2,4,6-trimethyl-3-cyclohexene carbaldehyde of the formula CHO have greenodors with an earthlike undertone, owing to which they are very suitablefor a.o. galbanum compositions.

3,812,059 Patented May 21., 1974 ice v British Patent Specification1,055,149 describes acetals of trialkyl substituted cyclic aldehydes ofthe formula CHO wherein R is an alkyl radical having 1 to 4 carbonatoms. These acetals have a strong fresh floral odor. However, nothingis said about the odor of the corresponding aldehydes with the exceptionof the odor of 3,5,6-trimethyl-3- cyclohexene carbaldehyde which isdescribed as green.

Dutch Pat. 110,190 mentions the preparation of an odorant material byDie1s-Alder-reaction of myrcenol with a dienophilic substance such asacrolein. The hydroxyaldehydes obtained, e.g.,4-(4-methyl-4-hydroxypentyl)-3- cyclohexene carbaldehyde of the formulaCHO have a floral. odor.

It has now been found that certain novel methyl substituted or2,5-methylene substituted, 6-n-propyl-3-cyclohexene carbaldehydes arevaluable perfumes, having spicy herbal odors, owing to which they canvery well be used in modern perfume compositions. Thus,2,4-dimethyl-6-npropyl-3-cyclohexene carbaldehyde, a compound of theformula CHO wherein R =R =CH and R =R =H has an intensively herbal rosyodor with a pepper touch, strongly reminiscent of geranium and wet roseleaves. The compound 4-methyl- 6-n-propyl-3-cyclohexene carbaldehyde,wherein R =CH and R =R =R =H is strong spicy with a tone of celerywhereas 2,5-methylene-6-n-propyl-3-cyclohexene carbaldehyde whereinR2i=R3=H and R and R together form -CH has a herbal odor connected withrosemary, aspic and sweet flag. I

The present compounds may, a.o., be prepared by a DielsAlder-reaction of2-hexene-1-al with suitable pentadienes and hexadienes such ascyclopentadiene, isoprene, 1,3-pentadiene or 2-methyl-l,3-pentadiene.The compounds may be obtained in the form of a mixture. Thus theproduction of 3,S-dimethyl-6-n-propyl-cyclohexene carbaldehyde of theformula The production of the 4-methyl compound of the formula CHO andthe 3-methyl compound of the formula H3O CHO may be expected together.Also the production of the 2-methyl compound of the formula CHO may beexpected together with the S-methyl compound of the formula CHO D.C3H1

The following examples are illustrative of this invention.

EXAMPLE I Preparation of 2,4-dimethyl-6-n-propy1-cyclohexenecarbaldehyde Into a 1 liter reaction flask, equipped with a stirrer,reflux condenser, dropping funnel, gas inlet tube and thermometer, 90 g.of 2-methyl-l,3-pentadiene and 1 g. zinc chloride are placed. Understirring and the introduction of nitrogen the contents of the flask arebrought to a reflux temperature of 75 C. Thereafter 95 g. of 2-hexene-l-al are added dropwise in a period of up to 1 hour underconditions of boil. The temperature of the contents of the flask risesto 120 C. After stirring for another half hour the reaction mixture iscooled to 20 C., after which 75 g. of toluene are added. The toluenesolution is washed in a separating funnel with a 5 percent sodiumbicarbonate solution until weakly basic to litmus and thereafter withwater until neutral. After drying, evaporation and fractionation 66 g.of 2,4-dimethy1-6-npropyl-cyclohexene carbaldehyde is obtained with aboiling point of 85 C. at 4 mm. Hg, n 1.4740. Most probably the compoundobtained is a mixture of the 2,4- and the 3,5-di-methyl compound.

If 1,3-pentadiene is reacted with hexene-I-al a mixture of 2-methyl andS-methyl-6-n-propyl-3-cyclohexene carbaldehyde is formed having aboiling point of 102-104" C. at 11 mm., n 1.4721.

in the reaction mixture. It is not necessary to use cyclopentadienemonomer because the dimer, dicyclopentadiene, is transferred into themonomer under the reaction conditions. The preparation proceeds asfollows:

Into a 250 m1. distillation flask, equipped with a reflux condenserdropping funnel, nitrogen inlet and thermometer is introduced 98 g. of2-hexene-l-al and g. dicyclopentadiene. The contents of the flask areheated to the boil under a nitrogen atmosphere and refluxed for 8 hours.The temperature of the reaction mixture rises from to 168 C. Thereafterthe contents of the flask are cooled down to 50 C. and fractionatedunder decreased pressure in a 40 cm. Vigreux column. There are obtained99 g. of 2,5 methylene-6-n-propyl-3-cyclohexene carbaldehyde with aboiling point of 103 C. at 3 mm. Hg, n 1.4808.

EXAMPLE III Perfume composition of the Fougere type Parts by weightEXAMPLE IV Perfume composition of the Rose" type Parts by weightPhenylethyl phenyl acetate 20 Phenylethyl salicylate 40 GeraniolPhenylethanol 240 Citronellol 150 Saudlewood oil E.I 20

Nonane diacetate-1,3 75 Geranyl acetate 50 Geranyl phenylacetate 20Citronellyl formiate 20 Phenylethyl acetate -25 Phenylethyl propionate60 Phenylacetaldehyde 50% in diethylphthalate 20 Phenylacetaldehyde1,3-butyleneglycol acetal 20 Eugenol l0 Methylisoeugenol 20a-Hexylcinnamic aldehyde 50 2,4-dimethyl 6 n-propyl 3 cyclohexenecarbaldehyde 10 EXAMPLE V Perfume composition of the Bouquet type Partsby weight Mnskus ambrette 20 Heliotropine 40 Benzyl acetate 1004-tert.butyl cyclohexyl acetate 80 a-Hexylcinnamic aldehyde 130a-Amylcinnamic aldehyde i 40 Linalyl acetate 30 Terpineol 80 Geranylacetate 80 Linalool 80 a-Methyl jonone 100 Methyl isoeugenol x 25Isoeugenol Geraniol 40 Phenylethanol 60 Styrallyl acetate Vetiverylacetate 50 IO-undecene-l-al 5 4-methyl 6 n-propyl 3cyclohexenecarbaldehyde 5 CHO n-GIHI wherein R R R and R are radicalsselected from the group consisting of CH H, and -CH when bridging R andR and wherein at least two of R R R and R are H.

2. The composition of claim 1 wherein said carbaldehyde is present in anamount of from 0.1-5.0 percent by weight.

3. The composition of claim 1 wherein said carbaldehyde is present in anamount of from 0.1-2.0 percent by weight.

4. The composition of claim 1 wherein said 6-propyl- 3-cyc1ohexenecarbaldehyde is 2,4-dimethy1-6-n-propyl-3- cyclohexene carbaldehyde.

5. The composition of claim 1 wherein said 6-pyropyl- 3-cyclohexenecarbaldehyde is 3,5-dimethyl-6-n-propyl-3- cyclohexene carbaldehyde.

6. The composition of claim 1 wherein said 6-propyl- 3-cyclohexenecarbaldehyde is 2-methyl-6-n-propyl3-cyclohexene carbaldehyde.

7. The composition of claim 1 wherein said 6-propyl-3- cyclohexenecarbaldehyde is 5-methyl-6-n-propyl-3-cyclohexene carbaldehyde.

8. The composition of claim 1 wherein said 6-propyl- 3-cyclohexenecarbaldehyde is 2,5-methylene-6-n-propyl- 3-cyclohexene carbaldehyde.

References Cited Gattefosse, Formulary of Perfumes and Cosmetics (1959),pp. 127, 128 and 129.

SAM ROSEN, Primary Examiner US. Cl. X.R. 260598

